Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4288—Polycondensates having carboxylic or carbonic ester groups in the main chain modified by higher fatty oils or their acids or by resin acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
  • C08G18/627—Polymers of hydroxylated esters of unsaturated higher fatty acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/46—Polyesters chemically modified by esterification
  • C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids

Definitions

• the present invention relates to a process for producing low-viscosity, air-drying binders which are suitable for the formulation of high-solids, fast-drying paints and architectural coatings.
• US Pat. No. 4,056,495 recommends the addition of aluminum alcoholates or chelates as additional drying agents, which is intended to overcome the disadvantages of the low molecular weight of the resins by means of increased crosslinking of the film.
• EP-PS 175 097 recommends the incorporation of diisocyanates which are half-capped with hydroxyethyl (meth) acrylate. This does not significantly accelerate drying.
• allyl ethers, in particular trimethylolpropane diallyl ether also leads to significantly lower-viscosity resins with drying that is also delayed compared to the conventional alkyd resins.
• binders produced by this process have high viscosities, although according to patent application EP 268 236 A 2, when using di-pentaerythritol and / or di-trimethylolpropane as the polyol component for the alkyd resin and very small proportions of alpha-beta-ethylenically unsaturated monomers, they are also low-viscosity Products are obtained which, based on their composition, have resulted in films which tend to be poorly drying and scratch-sensitive due to their composition.
• Patent application EP 267 562 A 2 describes alkyd resins which act as emulsifiers and in which the carboxyl groups which are essential for water-dilutability come from methacrylic acid units which, together with other vinyl and / or (meth) acrylic compounds, form part of the unsaturated ones before the alkyd resin preparation Fatty acids were grafted on.
• the invention further relates to the use of these binders for the formulation of high-solids, fast-drying paints and architectural coatings.
• the products according to the invention are notable for Varnish through faster drying and thorough drying, better film hardness and less tendency to wrinkle in layer thicknesses over 400 ⁇ m.
• unsaturated fatty acids with an iodine number above 130, preferably from 150 to 200, and with predominantly isolated double bonds are used, linseed oil fatty acid, safflower oil fatty acid and sunflower oil fatty acid being particularly suitable in practice.
• fatty acids with conjugated multiple double bonds as e.g. by artificial isomerization of fatty acid mixtures rich in linoleic acid or by dehydration of castor oil and subsequent ester cleavage, the grafting reaction may only take place to a minor extent (up to 20% by weight of the fatty acid portion used in this phase), since a larger portion leads to such high viscosities that it is not possible to formulate paints and architectural paints with a high solid content.
• the monomers used for the graft copolymerization with the fatty acids are essentially those vinyl and / or (meth) acrylic compounds which, besides the C-C double bond and optionally a carboxyl group, have no other functional group.
• examples of such monomers are aromatic vinyl compounds, such as styrene, para-methylstyrene, vinyltoluene, and (meth) acrylic esters of C1-C12 monoalcohols and vinyl esters of monocarboxylic acids, such as vinyl acetate and vinyl versatic acid.
• Monomer mixtures which give petrol-soluble copolymers are preferably used of para-methylstyrene, vinyl toluene and (meth) acrylic esters of C1-C12 monoalcohols.
• the graft copolymerization is carried out in such a way that the fatty acid is heated to 110-150 ° C. and the mixture of the monomers is metered in over the course of a few hours using a suitable initiator. The reaction mixture is then kept at the reaction temperature until a residue determination gives a polymerization conversion of over 95%.
• Peroxides whose decomposition temperature is above 80 ° C are particularly used as initiators, especially those which have a half-life of 1-2 hours in the temperature range between 120 ° C and 180 ° C, e.g. tert-butyl perbenzoate, di-tert-butyl peroxide, dicumyl peroxide, cumene hydroperoxide, tert-amyl peroxide.
• the fatty acid graft copolymers are composed of 20 to 60% by weight of the above-mentioned fatty acids, optionally 5 to 10% by weight of tetrahydrophthalic anhydride, optionally 1 to 8% by weight of methacrylic acid and 30 to 70% by weight of the above-mentioned vinyl and (meth) acrylic monomers, the sum of the percentages being 100.
• fatty acid graft copolymers prepared in this way are combined with other fatty acids, optionally aromatic and / or aliphatic monocarboxylic acids, Polyols, optionally polycarboxylic acids and optionally diisocyanates are converted into the binders according to the invention.
• Vegetable and animal fatty acids with an iodine number above 130 can be used as fatty acids in this stage, and conjugated double bonds can also be present.
• the following are suitable Sunflower oil, linseed oil, safflower oil and tall oil fatty acid, isomerized products of these fatty acids, as well as ricin fatty acid.
• Aromatic and / or aliphatic monocarboxylic acids are all products which are used for the production of alkyd resins, such as benzoic acid, p-tert-butylbenzoic acid, resin acids, such as abietic and levopimaric acid, and unsaturated monocarboxylic acids, such as crotonic acid and sorbic acid.
• Suitable polyols are those with a hydroxyl functionality of three to six, e.g. Trimethylolpropane, di-trimethylolpropane, pentaerythritol, di-pentaerythritol, sorbitol and similar sugar alcohols, and also hydroxyl-bearing heterocyclic compounds, such as trishydroxyethyl isocyanurate.
• polybasic carboxylic acids or their anhydrides examples include phthalic anhydride, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, isophthalic acid, terephthalic acid, dimer fatty acids, hexachloroendomethylenetetrahydrophthalic acid (HET-acid) and its anhydride, adipic acid and other aliphatic dicarboxylic acids, trimellitic anhydride and pyromellitic anhydride.
• diisocyanates such as tolylene diisocyanate
• phorone diisocyanate hexamethylene diisocyanate
• trimethylhexamethylene diisocyanate and their dimers can be used.
• the fatty acid graft copolymer, the fatty acids and the monocarboxylic acids with the polyols are esterified at 170-260 ° C. with azeotropic distillation using xylene as the circulating agent.
• Aromatic-free gasolines, propylene glycol ethers and C1-C4 alcohols are preferably used.
• the binders have an intrinsic viscosity (measured in chloroform at 20 ° C.) of 5.3 to 9.0 ml / g, preferably 6.0 to 8.0 ml / g, and are particularly suitable for the formulation of low-viscosity, high-solids Paintwork and architectural paints, their manufacture position with the usual pigments and additives is known to the person skilled in the art and requires no detailed explanation.
• the fatty acid graft copolymer (1) has an acid number of 80 mg KOH / g and an intrinsic viscosity (measured in chloroform at 20 ° C.) of 8.2 ml / g and is adjusted to 90% solids content for further processing with xylene.
• 500 parts (450 parts solid resin) of the fatty acid graft copolymer (1) are mixed with 260 parts of safflower oil fatty acid, 280 parts of an artificially isomerized sunflower oil fatty acid with 50% conjunct, 85 parts of p-tert-butylbenzoic acid, 150 parts of pentaerythritol and 25 parts of tetrahydrophthalic anhydride at 210 C with azeotropic distillation with xylene as a circulating agent up to an acid number of 10 mg KOH / g and then with 60 parts of isophorone diisocyanate at 100-110 ° C. up to an NCO content of 0 to form binder 1.
• the fatty acid graft copolymer (2) has an acid number of 103 mg KOH / g and an intrinsic viscosity (measured in chloroform at 20 ° C.) of 8.2 ml / g and is adjusted to 90% solids content for further processing with xylene.
• the fatty acid graft copolymer (3) has an acid number of 122 mg KOH / g and an intrinsic viscosity (measured in chloroform at 20 ° C.) of 8.2 ml / g and is adjusted to 80% solids content for further processing with xylene.
• 490 parts of the fatty acid graft copolymer (3) described in Example 3 are mixed with 450 parts of safflower oil fatty acid, 265 parts of an artificially isomerized sunflower oil fatty acid with 50% conjugate, 160 parts technical pentaerythritol with 12% dipentaery thrite content under azeotropic distillation at 210 ° C. up to an acid number of 12 mg KOH / g and then reacted with 70 parts of isophorone diisocyanate at 100-110 ° C. to an NCO content of 0 to give the binder 5. After distilling off the xylene under vacuum, the product obtained is dissolved in methoxypropoxypropanol.
• 70 parts of linseed oil fatty acid, 70 parts of sunflower oil fatty acid and 23 parts of xylene are heated to approx. 140 ° C and within 4 hours a mixture of 80 parts of para-methylstyrene, 54 parts of isobutyl methacrylate, 6 parts of n-butyl acrylate and 6 parts of di-tert.- butyl peroxide added as an initiator. After the addition has ended, the reaction temperature is maintained until a residue determination gives at least 95% polymerization conversion. If the reaction proceeds too slowly, 1 part of di-tert-butyl peroxide is added.
• the fatty acid graft copolymer (6) has an acid number of 102 mg KOH / g and an intrinsic viscosity (measured in chloroform at 20 ° C.) of 6.6 ml / g and is adjusted to 90% solids content for further processing with xylene.
• 700 parts (630 parts solid resin) of the fatty acid graft copolymer (6) are mixed with 260 parts safflower oil fatty acid, 350 parts an artificially isomerized sunflower oil fatty acid with 50% conjunct, 165 parts pentaerythritol and 220 parts hexachloroendomethylene tetrahydrophthalic acid reanhydride at 185 ° C with azeotropic distillation with xylene as a circulating agent up to an acid number of 10 mg KOH / g to binder 6. After distilling off the xylene under vacuum, the product thus obtained is dissolved in methoxypropoxypropanol.
• 210 parts of linseed oil fatty acid, 220 parts of sunflower oil fatty acid, 280 parts of ricinoleic acid, 83 parts of tetrahydrophthalic anhydride and 150 parts of pentaerythritol are esterified by azeotropic distillation at 210 ° C with xylene as a circulating agent up to an acid number below 5 mg KOH / g.
• xylene as a circulating agent up to an acid number below 5 mg KOH / g.
• After cooling to 135-140 ° C. 135 parts of para-methylstyrene, 63 parts of isobutyl methacrylate, 20 parts of methacrylic acid, 35 parts of methyl methacrylate and 9 parts of di-tert-butyl peroxide are added as initiator within 4 hours.
• White lacquers which are produced in a known manner according to the following recipe, are used for testing. 111.1 Resin, 90% in methoxypropoxypropanol 80.0 Titanium dioxide 5.0 Cobalt Siccativ, 1% Co 5.0 Lead Siccativ, 10% Pb 5.0 Calcium Siccativ, 2% approx 2.0 Anti-skin agent 0.5 Leveling agent; 0.25 parts solid content 6.2 White spirit 214.8 Lacquer, 85%
• Table 1 summarizes the test results of the paint test.
• Table 1 example Paint viscosity Pa.s non-sticky hours Drying hours Spreadability Wrinkle tendency 1 1.9 5 9 2nd no 2nd 1.4 4th 10th 1 no 3rd 1.0 4th 10th 1 no 4th 1.4 4th 9 2nd very weak 5 2.1 4th 12 2nd no 6 1.0 4th 10th 1 no A 4.0 8th 20th 5 very pronounced

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Life Sciences & Earth Sciences (AREA)
• General Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Paints Or Removers (AREA)
• Graft Or Block Polymers (AREA)
• Polyurethanes Or Polyureas (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Applications Claiming Priority (2)

Publications (2)

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Cited By (2)

Citations (3)

• 1988
  • 1988-09-23 AT AT234788A patent/AT390800B/de not_active IP Right Cessation
• 1989
  • 1989-09-18 EP EP19890117208 patent/EP0360188A3/fr not_active Withdrawn

Patent Citations (3)

Non-Patent Citations (1)

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